CN103429662A - Polymer electrolyte composition and dye-sensitized solar cell containing the same - Google Patents
Polymer electrolyte composition and dye-sensitized solar cell containing the same Download PDFInfo
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- CN103429662A CN103429662A CN2012800126795A CN201280012679A CN103429662A CN 103429662 A CN103429662 A CN 103429662A CN 2012800126795 A CN2012800126795 A CN 2012800126795A CN 201280012679 A CN201280012679 A CN 201280012679A CN 103429662 A CN103429662 A CN 103429662A
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- Prior art keywords
- polymer electrolyte
- electrolyte composition
- poly
- solar battery
- dye sensitization
- Prior art date
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- -1 poly(alkylene carbonate Chemical compound 0.000 claims abstract description 20
- 206010070834 Sensitisation Diseases 0.000 claims description 56
- 230000008313 sensitization Effects 0.000 claims description 56
- 239000002245 particle Substances 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 19
- 150000005846 sugar alcohols Polymers 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910020203 CeO Inorganic materials 0.000 claims description 2
- 239000011449 brick Substances 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 36
- 238000004519 manufacturing process Methods 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 16
- 239000003960 organic solvent Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 238000005191 phase separation Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 71
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 11
- 238000001879 gelation Methods 0.000 description 7
- 239000011244 liquid electrolyte Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000131 polyvinylidene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- JNVXRQOSRUDXDY-UHFFFAOYSA-N 1,1-diiodoethane Chemical compound CC(I)I JNVXRQOSRUDXDY-UHFFFAOYSA-N 0.000 description 1
- WIEPCLKFQFHUPU-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole;hydroiodide Chemical compound I.CCCN1CN(C)C=C1 WIEPCLKFQFHUPU-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPCXDBCEDWUSOU-UHFFFAOYSA-N benzoyl iodide Chemical compound IC(=O)C1=CC=CC=C1 WPCXDBCEDWUSOU-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- HEJPGFRXUXOTGM-UHFFFAOYSA-K iron(3+);triiodide Chemical compound [Fe+3].[I-].[I-].[I-] HEJPGFRXUXOTGM-UHFFFAOYSA-K 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- QKKCMWPOASMDQR-UHFFFAOYSA-J molybdenum(4+);tetraiodide Chemical compound I[Mo](I)(I)I QKKCMWPOASMDQR-UHFFFAOYSA-J 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003218 pyrazolidines Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- HUKGIVMVTNTTRT-UHFFFAOYSA-J silicon(4+) tetraiodate Chemical compound I(=O)(=O)[O-].[Si+4].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] HUKGIVMVTNTTRT-UHFFFAOYSA-J 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Abstract
Provided are a polymer electrolyte composition, a gel-type polymer electrolyte obtained by mixing the same at normal temperature, and a dye-sensitized solar cell containing the electrolyte. Since the poly(alkylene carbonate)-based polymer is included, a crosslinking process by radiation of heat or UV is not required when the polymer electrolyte is manufactured, such that a manufacturing process is simple. Accordingly, the polymer electrolyte is useful for mass production of a solar cell and maintained in a uniform state without a phase separation between two components due to excellent affinity between the polymer and the organic solvent included in the electrolyte, and has excellent electrode-electrolyte interface property in the solar cell due to an adhesive property of the gelled polymer electrolyte. A dye-sensitized solar cell containing the same as an electrolyte is capable of being used over a long period of time and maintaining stable conversion efficiency at a predetermined level or more.
Description
Technical field
The present invention relates to polymer electrolyte composition, by mixing the gel-type polymer electrolyte that described polymer electrolyte composition obtains in normal temps and containing described electrolytical dye sensitization solar battery.
Background technology
In 1991, by the dye sensitization solar battery of the research and development such as Gratzel of Switzerland, be to contain with titanium dioxide (TiO
2) as the photoelectrochemical cell (Nature of the semiconductor nanoparticle of main ingredient, dyestuff, ionogen and platinum counter electrode for absorbing solar ray, the 353rd volume, the 737th page, 1991), and its advantage is, for silicon solar cell, its low cost of manufacture, battery has transparent attribute, can manufacture flexible battery, and lower to the environmental change susceptibility.Dye sensitization solar battery and knownly utilize the silicon solar cell difference each other of p-n junction to be, carry out the absorption process of sun power and separate electronic hole to form the process of electric current in described known solar cell simultaneously, but in dye sensitization solar battery, absorption and the charge transfer process of sun power separate, by using dyestuff to absorb sun power, and by using semi-conductor with the electronic form transfer charge.
Due to it, to use the material of environmental sound and its production cost be silicon solar cell to dye sensitization solar battery 1/5, therefore as a kind of novel renewable energy resources with current cost of electricity-generating level, causes concern.Although dye sensitization solar battery has aforesaid lot of advantages, but consider the polarization of permanent stability, the toxicity produced by the leak of liquid of electrolytic solution and the solvent when the solar cell long term operation, still there are many serious problems in the commercialization of dye sensitization solar battery.Reason is because the ionogen used in dye sensitization solar battery comprises evaporating property organic solvent as acetonitrile.Therefore, need to develop the new polymers electrolyte that addresses the above problem and improve battery performance.The example of manufacturing the currently known methods of polymer dielectric comprise polymkeric substance is added into to liquid electrolyte with the method (Korean Patent No.10-0553337 and Korean Patent Publication No.10-2009-0107861) of carrying out physical gel thus and monomer or reactive oligomer be added into to liquid electrolyte implement the method (Korean Patent Publication No.2006-0118068 and 2007-0060960) of chemical gel to carry out polymerization.The problem of physical gel polymer dielectric is As time goes on phenomenon of phase separation may occur between polymkeric substance and organic solvent, and due to the adhesive power deficiency to metal oxide layer, therefore the resistance of the charge transfer reaction of the interface between electrode and ionogen increases, thereby has reduced electric current and efficiency performance.Simultaneously, monomer or oligomer are being added into during liquid electrolyte carries out the situation of gel with polymerization or crosslinking reaction, existence remains in the height possibility of the compounds such as initiator and linking agent added in crosslinked and polymerization process, and has reduced voltage or the current capability of described solar cell in described compound remains in ionogen the time.
Summary of the invention
An embodiment of the invention relate to that to provide a kind of polymer electrolyte composition, described polymer electrolyte composition to have excellent to the affinity that is included in the organic solvent in ionogen, ionic conductivity with to the adhesivity of electrode.
An embodiment of the invention relate to provides a kind of dye sensitization solar battery, consider the known dye sensitization solar battery that uses liquid electrolyte, dye sensitization solar battery of the present invention can make electrolytic solution volatilization or leak of liquid reduce to minimum, can use for a long time, and to keep stable efficiency of conversion more than predeterminated level.
One general aspect, comprise poly-(alkylene carbonates) based polyalcohol, high boiling solvent, redox derivative and the ceramic particle that contains the repeating unit that following formula 1 means for the polymer electrolyte composition of dye sensitization solar battery:
[formula 1]
Wherein, R is hydrogen atom; Have straight chain, ring-type or the branched-chain alkyl of 1 to 20 carbon atom, it can comprise assorted element, as oxygen, sulphur or nitrogen and fluorine; The aralkyl that perhaps there are 6 to 20 carbon atoms.
At the described polymer electrolyte composition for dye sensitization solar battery aspect general according to the present invention, the weight-average molecular weight of described poly-(alkylene carbonates) based polyalcohol is 1,000 to 1,0000,000 g/mol.
At the described polymer electrolyte composition for dye sensitization solar battery aspect concrete according to the present invention, described poly-(alkylene carbonates) based polyalcohol can be poly-(carbonic acid ethylidene ester), poly-(propylene carbonate), poly-(carbonic acid butylidene ester), poly-(plutonium carbonate polyhexamethylene) or their mixture or derivative.
At the described polymer electrolyte composition for dye sensitization solar battery according to a preferred aspect of the present invention, the content of described poly-(alkylene carbonates) based polyalcohol is 5 % by weight to 95 % by weight.
At this described polymer electrolyte composition for dye sensitization solar battery aspect general according to the present invention, described high boiling solvent can be one matter or the mixture that is selected from cyclic carbonate, lactone and normal temps melting salt.
At the described polymer electrolyte composition for dye sensitization solar battery aspect concrete according to the present invention, described high boiling solvent can be to be selected from carbonic acid ethylidene ester, propylene carbonate, their one matter or the mixture of cyclic derivatives, gamma-butyrolactone and ion type liquid.
At this described polymer electrolyte composition for dye sensitization solar battery aspect concrete according to the present invention, described redox derivative can provide the redox couple of I-/I3-.
At this described polymer electrolyte composition for dye sensitization solar battery aspect general according to the present invention, described ceramic particle can be to be selected from Al
2O
3, SiO
2, TiO2, SnO
2, CeO
2, ZrO
2, BaTiO
3, Y2O
3One matter or mixture with zeolite.
Aspect preferred, the median size of described ceramic particle can be 0.0001 μ m to 1,000 μ m.
Aspect preferred, the content of described ceramic particle can be 2 % by weight to 20 % by weight.
Polymer electrolyte composition of the present invention is by providing a kind of gel-type polymer electrolyte at the simple mixed processes of normal temps.
Another main aspect, dye sensitization solar battery comprises described ionogen.
When manufacturing according to the described polymer dielectric aspect this of the present invention, do not need the crosslinked operation of being undertaken by thermal radiation or UV radiation, make manufacture method simple.Therefore, described polymer dielectric can be used for the scale operation solar cell, and due to affinity excellent between the polymkeric substance comprised in described ionogen and organic solvent, thereby keep uniform state and do not occur being separated between two components, and due to the electrolytical adhesivity of gelation polymer, thereby there is excellent electrode-electric solution matter interface performance in solar cell.Contain the efficiency of conversion that described polymer electrolyte composition can be used for a long time as electrolytical dye sensitization solar battery and can be stable with maintenance more than predeterminated level.In addition,, therefore can manufacture and there is any control to the flexible solar battery of the size and dimension of predeterminated level for semi-solid state due to the solar cell made.
The accompanying drawing explanation
Fig. 1 under AM1.5 spectral filter condition embodiment 11 and 12 and comparative example 3 and 4 in manufacture be applied on dye sensitization solar battery of the present invention irradiate xenon (Xe) white light and 100mW/cm
2The current current-voltage curve figure that obtains of light.
Fig. 2 for by measure embodiments of the invention 12 and 14 and comparative example 3 and 4 in the graphic representation that obtains of the light conversion efficiency of the dye sensitization solar battery manufactured.
Embodiment
Of the present invention one general aspect, a kind of polymer electrolyte composition for dye sensitization solar battery comprises and contains poly-(alkylene carbonates) based polyalcohol that is expressed as the repeating unit of matrix polymer by following formula 1.
[formula 1]
Wherein, R is hydrogen atom; Have straight chain, ring-type or the branched-chain alkyl of 1 to 20 carbon atom, it can comprise assorted element, as oxygen, sulphur or nitrogen and fluorine; The aralkyl that perhaps there are 6 to 20 carbon atoms.
The carbonate group of the main chain of described polymkeric substance (OCOO) has carbon bond, and it is excellent making the affinity to carbonic ether or lactone group organic solvent.Therefore, when manufacture contains described carbonic ether as the described polymer dielectric of matrix polymer, do not pass and phenomenon of phase separation occurs in time between described polymkeric substance and described organic solvent, and guarantee to there is excellent mixed interface adhesion property between electrode and ionogen.Therefore, leak of liquid and volatilization do not occur in the described polymer dielectric that contains described polymeric matrix, and, when described polymer dielectric is applied to dye sensitization solar battery, can obtain high-level efficiency and excellent permanent stability.
In addition, when manufacturing described polymer dielectric, described matrix polymer can be by carrying out physical gel and polymerization or crosslinking reaction not occurring in the simple mixing of normal temps.
Particularly, linear carbonates, cyclic carbonate and lactone that described poly-(alkylene carbonates) based polyalcohol for example is used as the electrolyte solution of dye-sensitized solar cell electrolyte to organic solvent have excellent affinity, mutually mix even make described poly-(alkylene carbonates) based polyalcohol store for a long time simultaneously, phenomenon of phase separation also do not occur.In addition, because glass transition temp is low, so chain moves actively, guaranteed to be easy to the structure of transfer ions, makes the oxygen element be included in main chain help from the salt of separating in ionogen.
In addition, can induce described poly-(alkylene carbonates) based polyalcohol so that the electrolyte composition generation physical gel that contains described poly-(alkylene carbonates) based polyalcohol in dye sensitization solar battery, making can be in the situation that apply external heat and processes or offer extra crosslinking catalyst and form gel polymer electrolyte.Chemical crosslink reaction may be a factor that reduces the performance of solar cell, because initiator or catalyzer may be retained in ionogen as impurity.
Described poly-(alkylene carbonates) based polyalcohol is not particularly limited, but, in view of the dispersed of ceramic particle and gelation efficiency, can have and be preferably 1,000 to 1,000, the weight-average molecular weight of 000 g/mol.
The example of described poly-(alkylene carbonates) based polyalcohol meaned by formula 1 is unrestricted, but consider due to the high-affinity to organic solvent, phenomenon of phase separation do not occur, described poly-(alkylene carbonates) based polyalcohol can be preferably poly-(carbonic acid ethylidene ester), poly-(propylene carbonate), poly-(carbonic acid butylidene ester), poly-(plutonium carbonate polyhexamethylene) or their mixture or derivative.
Gross weight in described polymer electrolyte composition, the content of described poly-(alkylene carbonates) based polyalcohol comprised can be preferably 5 % by weight to 95 % by weight, when described content is less than 5 % by weight, it is insufficient that the gelation of electrolyte solution may be carried out ground, and when described content is greater than 95 % by weight, meeting forms hard gel but the movement velocity of ion reduces, and makes due to low ionic conductivity, and the efficiency of solar cell may be low.
Comprise solvent and redox derivative and described poly-(alkylene carbonates) based polyalcohol as electrolyte solution according to the described polymer electrolyte composition of a general aspect of the present invention.
Described solvent is a kind of high boiling solvent, and can be understood as term " high boiling solvent " and refer to that boiling point is higher than 150 ℃ in aforementioned and following description, and be preferably the organic solvent of 200 ℃ to 500 ℃ or at normal temps or 30 ℃ of salt to 100 ℃ of meltings.
Described solvent is unrestricted, as long as described solvent meets above-mentioned condition, and in view of for the high polarity of dissolved salt fully, the example of high boiling solvent can comprise carbonic ether, for example carbonic acid ethylidene ester or propylene carbonate and their cyclic derivatives; Organic solvent, for example lactone, for example gamma-butyrolactone; With the ion type liquid that contains imidazole salts or pyrazolidine salt.The material that is selected from described solvent can be used separately or use with the form of mixture.At this, the ionic salt that described ion type liquid exists with liquid state the normal temps of 30 ℃ to 100 ℃, and unlike the ionic salt compound that contains metallic cation and the common metalloid anion in the high-temperature fusion more than 800 ℃, the ionic salt existed with liquid state in the temperature below 100 ℃ is called ion type liquid, more specifically, the ion type liquid existed with liquid state in normal temps is called normal temps ion type liquid or normal temps melting salt.
Simultaneously, described redox derivative provides the redox couple of I-/I3-, and can be by iodine and diiodo-salt formation, and ion coexist cause reversible reaction.
Described salt compounded of iodine is unrestricted, and its example can comprise lithium iodide, sodium iodide, potassiumiodide, magnesium iodide, cupric iodide, iodate silicon, manganese iodide, molybdenum iodide, calcium iodide, ferric iodide, cesium iodide, zinc iodide, red mercury iodide, ammonium iodide, methyl-iodide compound, methylene radical iodide, ethyl iodide, ethylidene iodide, isopropyl iodide compound, isobutyl iodide compound, benzyl iodide compound, benzoyl iodide, allyl iodide compound, imidazoles iodide and 1-methyl-3-propyl imidazole iodide.
Consider ionic conductivity, the content of iodide salt is 0.01M to 10.0M, is preferably 0.1M to 1.0M.
In addition, in view of the high-level efficiency of guaranteeing solar cell, preferably, the content of described iodide is 0.01M to 0.1M.
Comprise described poly-(alkylene carbonates) based polyalcohol and electrolyte solution according to the described polymer electrolyte composition of a general aspect of the present invention, and further comprise ceramic particle to improve gelation, ionic conductivity and light scattering property.
Can add separately such as aluminum oxide (Al
2O
3), silicon oxide (SiO
2), titanium dioxide (TiO
2), SnO
2, CeO
2, ZrO
2, BaTiO
3, Y2O
3Add with the particle of zeolite or with the form of mixtures of two or more different substancess the example that is used as ceramic particle.The size of described ceramic particle is unrestricted, but at 0.0001 μ m to 1, between 000 μ m, is preferably 0.001 μ m to 1 μ m to guarantee dispersed and to control electrolytical thickness.
The content of the ceramic particle preferably, added is counted 2 % by weight to 20 % by weight with the gross weight of described electrolyte composition.When the content of ceramic particle is less than 2 % by weight, be difficult to show the effect of improving of ionic conductivity, and when described content is greater than 20 % by weight, the flexibility of gel polymer electrolyte reduces and, because the grumeleuse phenomenon of ceramic particle makes ionic conductivity again reduce, this improvement to the efficiency of solar cell causes adverse influence.
In addition, as long as can realize purpose of the present invention, polymer electrolyte composition of the present invention can further comprise known component, for example is included in the open circuit voltage dose (open voltage increasing agent) in the polymer dielectric of dye sensitization solar battery.
Polymer electrolyte composition of the present invention does not comprise for the initiator of chemical crosslink reaction and catalyzer etc., and can physical gel easily occur to manufacture gel-type polymer electrolyte in normal temps.
Described polymer dielectric can be as the ionogen of dye sensitization solar battery.
In the principle of work of dye sensitization solar battery, when solar ray is incident on battery, photon is absorbed by dyestuff.Dyestuff is in excited state, and electron motion is to TiO
2Conduction band, then move to electrode to flow through external circuit, this has generated electric energy.Dyestuff by accept from electrolytical with move to TiO
2The identical electronics of electron amount and in original state, the ionogen used is redox couple, iodide (I-)/triiodide (I3-) for example, and for accepting from the electronics of counter electrode and by redox reaction, described electronics being transported to dyestuff.The open circuit voltage of solar cell is by TiO
2Difference between semi-conductive fermi level and electrolytical redox level determines.
Manufacture dye sensitization solar battery and be not particularly limited with the method for implementing described principle of work, its example illustrates hereinafter.
Following dye sensitization solar battery is an example, wherein contain the optoelectronic pole of the dyestuff formed and counter electrode thereon toward each other, and the gel-type electrolyte distribution betwixt.
Specifically, optoelectronic pole comprises nano oxide layer, and wherein dyestuff is absorbed on transparency conductive electrode.Transparency conductive electrode is that the conductive oxide doped with for example indium oxide compound (FTO) of fluorine or indium tin oxide (ITO) is applied in such as the electrode on the transparent substrates of glass.Described substrate can be used transparent material without restriction, as long as this material is enough transparent in to allow solar rays incident, and can be made of plastics, for example polycarbonate or polyethylene carbonate.Nano oxide layer selects free titanium dioxide (TiO by containing one or more
2), tindioxide (SnO
2), zinc oxide (ZnO) and Tungsten oxide 99.999 (WO
3) composition of metal oxide in the group that forms makes, and be the layer of absorbing dye thereon.Preferably, the thickness of nano oxide layer is 5 μ m to 20 μ m.Can be by the solution absorbing dye that uses the ruthenium mixture or contain organic dye.This dyestuff can use the ruthenium mixture that absorbs visible rays as dyestuff, and can use any dyestuff, as long as can absorb visible rays electron emission effectively.
Use platinum catalyst to be formed on material on transparency conductive electrode as counter electrode.Can obtain in the following way platinum layer: the chloroplatinic acid (H that will contain the platinum that wherein dissolved
2PtCl
6) solution drips on transparency conductive electrode, carries out spin coating and 400 ℃ to the 600 ℃ thermal treatments of carrying out 10 minutes to 60 minutes.In addition, platinum layer can be by forming with sputtering method, chemical vapour deposition, vapor deposition process, thermal oxidation method and electrochemical plating etc.Here, be applied to the effect of catalyzer that platinum on counter electrode plays the reduction reaction of redox couple.
Contain that dyestuff is absorbed and after the platinum counter electrode is set to the optoelectronic pole of nano oxide layer respect to one another, gel-type polymer electrolyte be placed on therebetween making.
By stirred and in normal temps casting according to a polymer electrolyte composition aspect general of the present invention, can easily obtain gel-type polymer.
Can adopt thermoplastic film to come attached gel type polymer dielectric and two electrodes, and, when then at 60 ℃ to 120 ℃, keeping 5 seconds to 20 seconds with in conjunction with two electrodes the time placing thermoplastic film that thickness is 25 μ m to 60 μ m between two electrodes, can manufacture and contain integrated electrode and electrolytical dye sensitization solar battery each other.
Dye sensitization solar battery containing with good grounds polymer electrolyte composition of the present invention demonstrates excellent battery performance and wearing quality.
According to following examples, the present invention may be better understood, and these embodiment are used for illustration the present invention, and should not be construed as limiting the present invention.
Embodiment 1: the manufacture of polymer dielectric
The weight ratio of pressing 15:85 mix poly-(propylene carbonate) (weight-average molecular weight: 202,000) and electrolyte solution with the manufacture polymer dielectric.
Iodine (I by the lithium iodide of 0.5M (LiI), 0.05M
2) and the 4-tert .-butylpyridine of 0.5M be dissolved in carbonic acid ethylidene ester/gamma-butyrolactone mixed solvent (weight ratio is 50:50) to manufacture electrolyte solution used.
Use magnetic stirring apparatus after normal temps is mixed, by casting under the anhydrous atmosphere condition, making gel-type polymer electrolyte.
Embodiment 2: the manufacture of polymer dielectric
Except the weight ratio of poly-(carbonic acid ethylidene ester) and electrolyte solution is 20:80, the identical method manufacture gel-type polymer electrolyte with the said procedure with embodiment 1.
Embodiment 3 to 7: the manufacture of polymer dielectric
Further add the aluminum oxide (median size is 2nm to 4nm) as ceramic particle according to the content of table 1, described content is in the gross weight of the polymer electrolyte composition in embodiment 2, thereby makes gel-type polymer.
[table 1]
| Embodiment | Alumina content (% by weight) |
| 1 | 0 |
| 2 | 0 |
| 3 | 2 |
| 4 | 4 |
| 5 | 6 |
| 6 | 8 |
| 7 | 10 |
Embodiment 8
Manufacture gel-type polymer electrolyte according to the method identical with embodiment 4, difference is poly-(propylene carbonate) that (propylene carbonate) replacement weight-average molecular weight is 202,000 of gathering of using weight-average molecular weight to be 157,000.
Embodiment 9
The method identical according to embodiment 4 manufactured gel-type polymer electrolyte, and it is 75:25 with the ratio of mixture of electrolyte solution that difference is to gather (propylene carbonate).
Manufacture gel-type polymer electrolyte by the above-mentioned same program with embodiment 4, difference is to use the silicon-dioxide that the median size of 4.0 % by weight is 300 to replace aluminum oxide as ceramic particle.
Comparative example 1
Do not add poly-(propylene carbonate) that embodiment 1 uses and manufacture liquid electrolyte.
Comparative example 2
The method identical according to embodiment 1 manufactured polymer dielectric, difference is, when manufacturing gel polymer electrolyte, uses poly-(vinylidene fluoride-R 1216) multipolymer (weight-average molecular weight: 380,000, Kynar2801) replace gathering (propylene carbonate).
Test example 1
Appearance and the ionic conductivity of being separated between the electrolytical solvents that the gel-type polymer electrolyte of Evaluation operation example 1 to 10 acquisition and comparative example 1 and 2 obtain and polymkeric substance, degree of gelation, ceramic particle grumeleuse, and will the results are shown in following table 2.
[table 2]
In the explanation of table 1, * meaning that corresponding phenomenon does not occur, △ means that corresponding phenomenon occurs a little, and zero means that corresponding phenomenon occurs enthusiastically.
Embodiment 11 to 20: the manufacture of dye sensitization solar battery
(1) dyestuff absorbs the manufacture of titanium dioxide photoelectrode
The butanol solution that will wherein be dissolved with the titanium isopropylate (IV) of 2 % by weight by spin coating is applied in the electrically conducting transparent substrate of the Indium sesquioxide (FTO) that is coated with doped with fluorine, then at 450 ℃, carries out thermal treatment in 30 minutes to form blocking layer.Employing is scraped the coating composition (Ti-Nanoxide T20/SP, Solaronix) that the skill in using a kitchen knife in cookery will contain titanium dioxide and is put on transparency conductive electrode, and carries out thermal treatment in 30 minutes at 450 ℃ and have the TiO of 10 to 15 μ m thickness with formation
2Nano oxide layer.N719 (Solaronix by 0.3mM, Co., Ltd., it is ruthenium base light-sensitive coloring agent) and cis-diisothiocyanic acid-bis-(2,2'-bipyridyl-4, the 4'-dicarboxylic acid) ruthenium (II) two (tertiary butyl ammoniums) is dissolved in the mixed solvent (weight ratio is 50:50) of acetonitrile and the trimethyl carbinol, to make dye solution.By prepared TiO
2Electrode is immersed in wherein 18 hours in 30 ℃, then dry, makes dyestuff and absorbs titanium dioxide photoelectrode.
(2) manufacture of platinum counter electrode
To wherein be dissolved with the chloroplatinic acid (H of 0.01M by spin coating
2PtCl
6) aqueous isopropanol be applied in the transparent conducting glass substrate that is coated with FTO, then at 450 ℃, carry out thermal treatment in 30 minutes, make the platinum counter electrode that is coated with platinum layer.
(3) manufacture of solar cell
By dyestuff absorb titanium dioxide photoelectrode and the platinum counter electrode positioned opposite to each other after, the gel polymer electrolyte that will make in embodiment 1 to 10 by castmethod is provided between two electrodes.After the heat fusing film that will have 25 μ m thickness is placed between two electrodes, 90 ℃ of heating 10 seconds with in conjunction with two electrodes.By they in 50 ℃ aging 1 hour, finally make and contain integrated electrode and electrolytical dye sensitization solar battery each other.
Comparative example 3
The step identical according to embodiment 11 manufactured dye sensitization solar battery, and difference is, only will be used for ionogen at the electrolyte solution of comparative example 1 acquisition.
Comparative example 4
The step identical according to embodiment 11 manufactured dye sensitization solar battery, and difference is, the polymer dielectric obtained in comparative example 2 is used for to ionogen.
Test example 2
At 100mM/cm
2The condition of incident light under, use the battery performance of the dye sensitization solar battery made in xenon white light and AM1.5 spectral filter Evaluation operation example 11 to 20 and comparative example 3 and 4.The example of the current-voltage curve of resulting dye sensitization solar battery is presented in Fig. 1, and is described in following table 3 from short-circuit current density (JSC), open circuit voltage (VOC), the packing factor (FF) of estimating graphic representation and the efficiency value of being calculated by opisometer.
Example shown in Fig. 1 relate to embodiment 11 and 11 and comparative example 3 and 4 in the solar cell that obtains.
[table 3]
From the results shown in Table 3, along with rising, short-circuit current density and the decrease in efficiency of the content of polymkeric substance contained in polymer dielectric.Reason is the ionic conductivity decline due to polymer dielectric, thereby has reduced the movement velocity of the ion existed in the ionogen.
Can find out the semi-solid dye sensitization solar battery of short-circuit current density and efficiency and the polymer dielectric that applies embodiment equally high in the situation of comparative example 3 (it is the example of dye sensitization solar battery that applies the liquid electrolyte of comparative example 1).
Simultaneously, with the situation of the polymer dielectric that applies embodiment, compare, dye sensitization solar battery (comparative example 4) efficiency of polymer dielectric (it is the polymkeric substance (poly-(vinylidene fluoride-R 1216) multipolymer) of polymeric matrix to replace polymeric matrix of the present invention applied as known dye sensitization solar battery) that applies comparative example 2 is low.
In addition, in the situation that polymer dielectric comprises the ceramic particle with nano-scale, with contrary situation, compare, efficiency is improved, and can find out when content is 4 % by weight most effective.
Simultaneously, passing in time, the efficiency of the dye sensitization solar battery that measurement is manufactured in embodiment 12 (polymer dielectric that comprises embodiment 2), embodiment 14 (polymer dielectric that comprises embodiment 4) and comparative example 3 and 4, to detect the stability of passing in time of dye sensitization solar battery, and result is presented in Fig. 2.
By Fig. 2, with the dye sensitization solar battery (comparative example 3) that uses liquid electrolyte, compare, the starting efficiency of the dye sensitization solar battery that the employing solid polymer electrolyte is manufactured is slightly low, more stable but solar cell properties is passed in time.Particularly, with the liquid-type dye sensitization solar battery (comparative example 3) that keeps 81% starting efficiency with adopt and gather the dye sensitization solar battery that (vinylidene fluoride-R 1216) co-polymer based polymer electrolyte makes (embodiment 4,84% starting efficiency) compare, in the situation of the semi-solid type dye sensitization solar battery made in embodiment 14, keep afterwards 98% starting efficiency at 10 days, and show excellent permanent stability.The above results is because electrolyte solution generation gelation, and between two components because polymkeric substance keeps uniform state not to be separated to the excellent affinity of organic solvent, electrolyte solution is subject to the constraint of polymer dielectric.As a result, with liquid electrolytic plastome, compare, the leak of liquid loss of battery descends, thereby guarantees that performance is more stable.Therefore, by polymer dielectric is put on to dye sensitization solar battery and has improved significantly permanent stability.
Claims (13)
1. the polymer electrolyte composition for dye sensitization solar battery, described composition comprises:
Poly-(alkylene carbonates) based polyalcohol that contains the repeating unit meaned by following formula 1;
High boiling solvent;
The redox derivative;
And ceramic particle:
[formula 1]
Wherein, R is hydrogen atom; Have straight chain, ring-type or the branched-chain alkyl of 1 to 20 carbon atom, it can comprise assorted element, as oxygen, sulphur or nitrogen and fluorine; The aralkyl that perhaps there are 6 to 20 carbon atoms.
2. polymer electrolyte composition as claimed in claim 1, wherein, the weight-average molecular weight of described poly-(alkylene carbonates) based polyalcohol is 1,000 to 1,0000,000.
3. polymer electrolyte composition as claimed in claim 1, wherein, described poly-(alkylene carbonates) based polyalcohol is poly-(carbonic acid ethylidene ester), poly-(propylene carbonate), poly-(carbonic acid butylidene ester), poly-(plutonium carbonate polyhexamethylene) or their mixture or derivative.
4. polymer electrolyte composition as claimed in claim 1, wherein, the content of described poly-(alkylene carbonates) based polyalcohol is 5 % by weight to 95 % by weight.
5. polymer electrolyte composition as claimed in claim 1, wherein, described high boiling solvent is one matter or the mixture that is selected from cyclic carbonate, lactone and normal temps melting salt.
6. polymer electrolyte composition as described as claim 1 or 5, wherein, described high boiling solvent is to be selected from carbonic acid methylene radical ester, carbonic acid ethylidene ester, propylene carbonate, their one matter or the mixture of cyclic derivatives, gamma-butyrolactone and ion type liquid.
7. polymer electrolyte composition as claimed in claim 1, wherein, described redox derivative provides the redox couple of I-/I3-.
8. polymer electrolyte composition as claimed in claim 1, wherein, described ceramic particle is to be selected from Al
2O
3, SiO
2, TiO
2, SnO
2, CeO
2, ZrO
2, BaTiO
3, Y2O
3One matter or mixture with zeolite.
9. polymer electrolyte composition as described as claim 1 or 8, wherein, the median size of described ceramic particle is 0.0001 μ m to 1,000 μ m.
10. polymer electrolyte composition as described as claim 1 or 8, wherein, the content of described ceramic particle is 2 % by weight to 20 % by weight.
11. the gel-type polymer electrolyte for dye sensitization solar battery, described gel-type polymer electrolyte requires 1 described polymer electrolyte composition to obtain in normal temps, to carry out gel by hybrid right.
12. a dye sensitization solar battery, described power brick contains:
Polymer electrolyte composition claimed in claim 1.
13. a dye sensitization solar battery, described power brick contains:
The described gel-type polymer electrolyte of claim 11.
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| KR1020110027972A KR101406985B1 (en) | 2011-03-29 | 2011-03-29 | Polymer electrolytes composition and dye-sensitized solar cells containing the same |
| PCT/KR2012/002274 WO2012134166A2 (en) | 2011-03-29 | 2012-03-28 | Polymer electrolyte composition and dye-sensitized solar cell containing the same |
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| CN105143387B (en) * | 2013-09-10 | 2017-05-24 | Lg化学株式会社 | Resin composition comprising polyalkylene carbonate and self-adhesive film produced therefrom |
| KR101519786B1 (en) * | 2014-04-30 | 2015-05-12 | 상명대학교 천안산학협력단 | Gel electrolyte compositions for printing at room temperature and dye-sensitized solar cells using the same |
| IL280849B1 (en) * | 2018-09-21 | 2024-04-01 | Ambient Photonics Inc | Dye sensitized photovoltaic cells |
| CN112495441A (en) * | 2020-11-27 | 2021-03-16 | 华南理工大学 | Cerium dioxide coated ZIF-67 catalyst for synthesizing cyclic carbonate and preparation thereof |
| KR20220092437A (en) * | 2020-12-24 | 2022-07-01 | 주식회사 엘지에너지솔루션 | Composition for electrolyte of lithium secondary battery, gel polymer electrolyte and lithium secondary battery comprising the same |
| US20230335792A1 (en) * | 2020-12-24 | 2023-10-19 | Lg Energy Solution, Ltd. | Composition for electrolyte of lithium secondary battery, gel polymer electrolyte, and lithium secondary battery including gel polymer electrolyte |
| WO2022139543A1 (en) * | 2020-12-24 | 2022-06-30 | 주식회사 엘지에너지솔루션 | Composition for electrolyte of lithium secondary battery, gel polymer electrolyte and lithium secondary battery comprising same |
| EP4310972A1 (en) * | 2022-03-29 | 2024-01-24 | Lg Energy Solution, Ltd. | Gel polymer electrolyte composition having reduced crosslinking time, secondary battery comprising same, and method for manufacturing secondary battery |
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- 2012-03-28 CN CN201280012679.5A patent/CN103429662B/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101406985B1 (en) | 2014-06-17 |
| WO2012134166A3 (en) | 2013-01-03 |
| US8900483B2 (en) | 2014-12-02 |
| KR20120110235A (en) | 2012-10-10 |
| EP2691463A4 (en) | 2015-03-04 |
| CN103429662B (en) | 2016-03-02 |
| WO2012134166A2 (en) | 2012-10-04 |
| JP2014514699A (en) | 2014-06-19 |
| EP2691463A2 (en) | 2014-02-05 |
| US20130075666A1 (en) | 2013-03-28 |
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